JPS6021122B2 - Funaku beetle control agent - Google Patents

Description

[Detailed description of the invention] TECHNICAL FIELD The present invention relates to a funaku insect control agent.

More specifically, this invention relates to general formula (1): [wherein R,
represents an allyl group, a cyclohexyl group, a phenylalkyl group optionally substituted with a halogen atom (however, the number of carbon atoms in the alkyl portion is 1 or 2), or a lower alkyl group having 1 to 4 carbon atoms, R2 is an allyl group, a cyclohexyl group , a phenylalkyl group (however, the number of carbon atoms in the alkyl moiety is 1 or 2), an alkyl group having 1 to 12 carbon atoms, or a lower terminal substituted with a hydroxyl, carboxylic, sulfonate, N,N-jethylamino or morpholino group The present invention relates to a pest control agent for sea bream insects, which contains as an active ingredient one or more of compounds represented by (representing an alkyl group) or possible salts of these compounds.

Funakuimushi taxonomically belongs to the Funakuhidae family of the bivalve mollusk family, and there are many types of funakuimushi.

Most species have a distribution restricted to relatively narrow bodies of water, but some species include Teredonav
Some species, such as A. alis), are distributed almost worldwide. These sea bream beetles live by boring into all kinds of wood in the sea, such as wood from lumber yards, the bottoms of wooden ships, and the piers of wooden piers. In other words, its life involves penetrating an oblong-shaped hole into the wood, communicating with the outside world only through a small hole, and when external conditions become unfavorable, it pulls a water pipe into the hole and uses a pallet to drill the hole instead. It is resistant to external conditions because it closes its mouth. The damage caused by these sea bream beetles is enormous, and major incidents have even occurred not only in Japan but also around the world. Particularly in Japan, it has become common practice in recent years to store wood in seawater, but no suitable method has been found to prevent damage from sea bream beetles. The inventors of the present invention have considered ways to control the funaku beetles using drugs, and as a result of testing a large number of drugs, they have found that the compound of the present invention can be specifically and extremely effectively applied to the funa beetles.

This family of compounds has traditionally been used as agricultural fungicides and insecticides, and their activity against terrestrial insects has been shown to be
It is known from Special Publication No. 33-625 and Achieve der Farmazzie 293 957-96 Sword Page ('65), etc., but its living function is significantly different from that of sea-dwelling beetles that bore holes in wood. As far as the inventor of this invention knows, there is no known physiological effect on the sea bream beetle. In R of the above general formula (1), examples of the lower alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t
-butyl group and sec-butyl group. Examples of the phenyl alkyl group include a penzyl group and a phenethyl group. On the other hand, examples of the alkyl group having 1 to 12 carbon atoms in R2 of the monopronged formula (1) include methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, lauryl group, etc., and branched chains thereof. Examples include groups.

Further, examples of the phenylalkyl group include a penzyl group and a phenethyl group. Possible salts of the compound of general formula (1) include sodium salts, potassium salts, ammonium salts, and substituted ammonium salts when the substituent contains an acidic group; In some cases, there are hydrochlorides, etc.

The method for producing the compound of general formula (1) generally includes R, and R2
are the same group, two equivalents of amine (R, -NH
The target compound can be obtained by reacting 2) with 1 equivalent of carbon disulfide to form a dithiocarbamic acid amine salt, and then reacting with 2 equivalents of formaldehyde.

When R and R2 are different groups, for example, amine (R, -NH2) is reacted with carbon disulfide and sodium hydroxide to form dithiocarbamate sodium salt, and then amine hydrochloride (R2 -NH2 HCI) and 2 equivalents of formaldehyde to obtain the desired compound.

[Arts Naimitztel Huoschunk No. 19 Indigo (11
No.), pp. 1809 to 1819 (196 Hanno)] Specific examples of preferred compounds used in the present invention include 3,
5-dimethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-methyl-5-ethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-methyl-5-allyl-tetrahydro-1,3,5 -Thiadiazine-2-thione, 3-methyl-5-amyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-methyl-5-octyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-methyl- 5-lauryltetrahydro-1,3,5-thiadiazine-2-thione,
3-methyl-5-benzyltetrahydro 1,3,5
-thiadiazine-2-thione, 3-methyl-5-(4-chlorobenzyl)-tetrahydro-1,3,5-thiadiazine-2-thione, 3-methyl-5-phenethyl-tetrahydro-1,3,5-thiadiazine-2-thione,
3-methyl-5-(2-hydroxyethyl)natrahydro-1,3,5-thiadiazine-2-thione, 3-methyl-5-carboxymethyl-tetrahydro-1,3,
5-thiadiazine-2-thione, 3-methyl-5-cyclohexyltetrahydro-1,3,5-thiadiazine-2-thione, 3-methyl-5-morpholinomethyl-tetrahydro-1,3,5-thiadiazine-2-thione,
3,5-diethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-ethyl-5-methyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-ethyl-5-allyl-tetrahydro-1, 3,5-thiadiazine-2-thione, 3-ethyl-5-amyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3
-ethyl-5-octyl-tetrahydro-1,3,5-
Thiadiazine-2-thione, 3-ethyl-5-lauryl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-ethyl-5-benzyl-tetrahydro-1,3
, 5-thiadiazine-2-thione, 3-ethyl-5-(
4-chlorobenzyl)-tetrahydro-1,3,5-thiadiazine-2-thione, 3-ethyl-5-phenethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-ethyl-5-(2-hydroxyethyl)-7-trahydro-1,3 , 5-thiadiazine-2-thione, 3
-ethyl-5-carboxymethyl-tetrahydro-1,
3,5-thiadiazine-2-thione, 3-ethyl-5-
Cyclohexyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-ethyl-5-morpholinomethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3,5-diisopropyl-tetrahydro-1,3,
5-thiadiazine-2-thione, 3,5-di-n-butyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-n-butyl-5-furyl-tetrahydro-1
, 3,5-thiadiazine-2-thione, 3-n-butyl-5-amyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-n-butyl-5-octyl-tetrahydro-1,3,5-thiadiazine-2 -thione, 3
1-n-butyl-5-lauryl-tetrahydro 1,3,
5-thiadiazine-2-thione, 3-sec-butyl-
5-benzyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-n-butyl-5-phenethyl-tetrahydro-1,3,5-thiadiazine-2-thione,
3-n-butyl-5-(2-hydroxyethyl)-tetrahydro-1,3,5-thiadiazine-2-thione, 3
-n-butyl-5-carboxymethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-n-butyl-5-cyclohexyl-tetrahydro-1,3,5-
Thiadiazine-2-thione, 3-rt-butyl-5-
Morpholinomethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3,5-dicyclohexyru-tetrahydro-1,3,5-thiadiazine-2-thione, 3
-cyclohexyl-5-methyl-tetrahydromount 1,3
, 5-thiadiazine-2-thione, 3-cyclohexyl-5-aryl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-cyclohexyl-5-lauryl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-cyclohexy-5-penzyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-cyclohexy-5-phenethyl-tetrahydro-1,3,5-
Thiadiazine-2-thione, 3-cyclohexyl-5-(2-hydroxyethyl)-tetrahydro-1,3,5
-thiadiazine-2-thione, 3-cyclohexyl-5
- Ruboxymethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-(4-fluorophenethyl)-5-methyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-(4-fluorophenethyl)-5-methyl-tetrahydro-1,3,5-thiadiazine-2-thione .

lofuenethyl)-5-aryltetrahydro 1,3,
5-thiadiazine-2-thione, 3-phenethyl-5-
n-lauryl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-phenethyl-5-benzyrutetrahydro-1,3,5-thiadiazine-2-thione, 3
-phenethyl-5-cyclohexyltetrahydro 1
, 3,5-thiadiazine-2-thione, 3-(3,4-
dichlorophenethyl)-5-(3-hydroxypropyl)-tetrahydro-1,3,5-thiadiazine-2-thione, 3-(2,4-dichlorophenethyl)-5-carbosimethyl-tetrahydro-1,3, 5-thiadiazine-2-thione, 3-phenethyl-5-N,N-diethylami/ethyl-tetrahydro-1,3,5-thiadiazine-2-thione hydrochloride, 3-phenethyl-5-potatiosulfoethyl-tetrahydro-1,3,5-thiadiazine -2-thione, 3,5-diphenethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3,5-dibenzyl-tetrahydro-1,3,5-thiadiazine-
2-thione, 3-benzyl-5-methyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-benzyl-5-ethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-penzyl-5-butyl-tetrahydro- 1,3,5-thiadiazine-2-thione, 3-benzyl-5-aryl-tetrahydro 1,3,5-thiadiazine-2-thione, 3-(3-prombenzyl)
15-(2-hydroxyethyl)-tetrahydro 1,
3,5-thiadiazine-2-thione, 3-(4-fluorobenzyl)-5-(3-hydroxypropyl)-tetrahydro-1,3,5-thiadiazine-2-thione, 3
-(3,4-dichlorobenzyl)-5-sodiocarboxymethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-(3,4-dichlorobenzyl)-5-
N,N-diethylaminoethyl tetrahydride.

-1,3,5-thiadiazine-2-thione hydrochloride, 3-
Penzyl-5-triethylammoniumcarboxymethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-penzyl-5-potatiosulfoethyl-tetrahydro-1,3,5-thiadiazin-2-ion, 3
-benzyl-5-cyclohexyltetrahydro-1,
3,5-thiadiazine-2-thione, 3-benzyru5
-morpholinomethyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3,5-diaryl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-allyl-5-methyl-tetrahydro-1,3,5 -thiadiazine-2-thione, 3-allyl-5-methyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-allyl-5-methyl-tetrahydro-1,3,
5-thiadiazine-2-thione, 3-furyl-5-cyclohexyl-tetrahydro-1,3,5-thiadiazine-2-thione, 3-aryl-5-morpholinomethyl-tetrahydro-1,3,5-thiadiazine-2-thione,
etc.

The compound used in the present invention has a very effective effect on preventing the adhesion of sea bream larvae, and the amount used is usually 0.
．． A concentration of about 0.001 to 1 skin level is preferable.

An example of a treatment method is to surround the sea with simple objects.
A chemical is added to the lumber to a predetermined concentration, and the lumber in the wood storage is soaked in it, usually for 1 to 2 days, and then transferred to the lumber storage area.

The compound of the present invention used therein may be dispersed in a suitable solvent such as water, alcohol, acetone, etc. so as to be uniformly dispersed in seawater.
Preferably, it is dissolved or emulsified in an organic solvent such as xylene, dimethylformamide, methyl cellosolve, etc., and prepared by adding a surfactant if necessary. In this case, the surfactants include higher fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene polyoxypropylenes, and alkyltrimethylammonium salts. , alkylbetaines, etc.
Alternatively, the compound of the present invention may be made into a jelly using a polymeric substance that forms a gel-like substance, or the compound of the present invention may be adsorbed or kneaded into a porous polymeric substance and molded, and then immersed in a trench in a seawater lumber storage area. Alternatively, by gradually dissolving it into seawater by incorporating it into a mold, it is possible to prevent the adhesion of sea bream beetles.

In order to make a jelly from the compound of the present invention, the compound of the present invention is added in an amount of 3 to 20% by weight, and the polymer substance that forms a gel-like substance is added in an amount of 5 to 20% by weight.
%, organic solvent 1-10%, or surfactant 1-1%
The organic solvent prepared to contain 0% and the remaining amount are made into a jelly using water. In addition, in order to adsorb the compound of the present invention to a porous polymeric substance, 0.5 to 1 part by weight of the compound of the present invention should be added to 1 weight of the porous polymeric substance; 0.5 to 1 part by weight of the compound of the invention, 0.05 to 2 parts by weight of the surfactant; and also 1 part by weight of the porous polymeric material, of the compound of the invention. 0.5 to 10 parts by weight, organic solvent 0.
5 to 10 parts by weight; and also 0.5 to 1 part by weight of the compound of the present invention, 0.05 to 2 parts by weight of a surfactant, and 0.5 to 10 parts by weight of an organic solvent per 1 part by weight of a porous polymeric substance. It is desirable that the combination be such that the surface of the polymer substance after drying is solidified to the extent that it does not become too sticky.

The polymeric substances that form the jelly used here include polyacrylates, polyacrylamide, polyethylene oxide, polymethacrylates, polyvinyl alcohol and their copolymers, carboxymethyl cellulose, gelatin, etc. It will be done. Porous polymer materials include polyethylene, polypropylene, polyurethane,
Examples include organic synthetic polymers such as polystyrene; natural polymers such as cotton, or rather, fineboard, and inorganic materials such as glass fiber and asbestos. Examples of organic solvents include methanol, acetone, xylene/kerosene, dimethylformamide, methyl cellosol, and ethylene glycol.

In addition, the surfactants used here include higher fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene polyoxypropylenes, alkyltrimethylammonium Examples include salt and alkyl betaines. Next, when the compound of the present invention is injected into wood to prevent the attack of sea bream beetles, a solution of the compound of the present invention dissolved or dispersed in a solvent or a mixture of the compound of the present invention and a natural resin, oily synthetic resin, or synthetic rubber may be used. A vehicle, a plasticizer, a surfactant, a solvent, and optionally a coloring pigment are added, and a solution is used which is dissolved, dispersed, emulsified, or thoroughly kneaded.

The natural resin, oil-based synthetic resin or synthetic rubber vehicle mentioned here includes rosin, boiled oil, chlorinated rubber, alkyd resin, vinyl resin such as vinyl chloride and pinyl acetate,
Acrylic resin, polyolefin resin such as polybutene,
Examples include polystyrene, various synthetic rubbers, polyurethane resins, epoxy resins, unsaturated polyester resins, phenolic resins, coal tar, and the like.

Typical compounds used in this invention and their properties are listed in Table 1.

Table 1 Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

Example 1 5 parts of each compound were formulated with 9 parts of dimethylformamide and 5 parts of polyethylene glycol fatty acid ester, and diluted with seawater to prepare a test solution.

20 to 30 Funakimushi larvae were collected from the Funakimushi breeding tank using a plankton net and placed into a thick glass tube with a diameter of 6 mm and a height of 100 ribs, into which NXX-10 Mufu gauze was attached. , each compound was immersed in a test solution of each concentration for 8 hours, and then reared for 4 hours in a running clear seawater aquarium, and the number of surviving and dead larvae was counted under a retrospective microscope. The results of determining the % lethal concentration are shown in Table 2.

Table 2 Example 2 Test materials (30 skins x 6 skins x 2 c
) was immersed in the sea for about two months, and the drug was tested using the test material that was made by sea funk beetles (mainly Teredo navalis) making holes in the test material.

That is, the test material was brought back from the sea, kept in clear seawater for 5 days, measured the number of water tubes on one side of the material, and then exposed to the chemical for 4 hours. After contact, the test material was thoroughly washed with seawater. ,
After rearing in clear seawater for 5 days, the number of water tubes on one side was counted again to determine the effect of the drug. In this case, the conditions were the same during each breeding and drug contact, and the seawater temperature was maintained at 20 to 2y0, and aeration was performed. The results are shown in Table 3. Table 3 Example 3 1 part of the compound of the present invention, 5 parts of dimethylformamide, 5 parts of surfactant, and 15 parts of polyacrylamide were mixed,
10k9 made into a jelly with 5 parts water was placed in a plastic basket and hung in a seawater lumber storage area during the adhesion period of the sea bream.

That is, a 4 square raft is vertically arranged in two rows with a spacing of 0.5 skin, and three jelly products of the present invention are hung between them at a spacing of 4, lm and 1.5 cm from that position. 5 Hang the test panel on the skin and measure the degree of adhesion and perforation of the sea bream after 2 months by
The results of the investigation using line photographs are shown in Table 4. Table 4 Example 4 Next, a formulation example for injecting the compound of the present invention into wood is as follows.

Formulation Example 1 Formulation Example 2 Compound No. 1 10 shots Compound No. 7 10% rosin 5% copper naphthenate 10% dimethylform. Bolibutene 3*amide 85
% dimethylform 77 amide The above chemical solution was JIS-
Wood pieces (30 × 6 skins × 2 skins) according to the method of A9301
After being injected into the water and immersed in the sea for one year, the effectiveness against sea breams was determined using X-ray photographs.

The results are shown in Table 5. Table 5

Claims (1)

[Claims] 1 General formula (I): ▲ Numerical formulas, chemical formulas, tables, etc.
However, the number of carbon atoms in the alkyl part is 1 or 2) or 1 carbon number.
~4 lower alkyl group, R_2 is an allyl group, a cyclohexyl group, a phenyl alkyl group (however, the number of carbon atoms in the alkyl portion is 1 or 2), an alkyl group having 1 to 12 carbon atoms, or hydroxyl, carboxyl, sulfonate, N
, a lower alkyl group terminally substituted with an N-diethylamino or morpholino group) or one or more possible salts of these compounds as an active ingredient. agent.